Organic carbon and nitrogen fixed in illite (I) clays were identified in a hydrothermal breccia structure from the Harghita Bãi area of the Neogene volcanism of the East Carpathians. The potassium-illite (K-I) alteration related to an early magmatic-hydrothermal event (9.5 ± 0.5 Ma) was later replaced by ammonium-illite (NH4-I) (6.2 ± 0.6 Ma) owing to circulation of an organic-rich fluid. Several textural evolutions of breccia structures were recognized, such as ‘shingle’, ‘jigsaw’, ‘crackle’ and hydraulic in situ fractures. The high-field-strength element behaviours of the K-I and NH4-I argillic altered andesite are close to chondritic ratios, indicating no contribution of hydrothermal fluid, especially on NH4-I andesite alteration and the CHArge-and-RAdius-Controlled (CHARAC) behaviour within silicate melts. The rare earth element normalized patterns show two distinct trends, one with a Eu* anomaly (K-I) and the other with a Nd* anomaly (NH4-I), indicating a boundary exchange with the organic-rich fluid. The strongly depleted δ13C (V-PDB) measured for the NH4-I clays reflects values (−24.39 to −26.67 ‰) close to CH4 thermogenic oxidation, whereas the δ15N (‰) from 4.8 to 14.8 (± 0.6) confirmed that the N2 originated from post-mature sedimentary organic matter. The last volcanism (6.3 to 3.9 ± 0.6 Ma) and simultaneous volcano-induced tectonics in the proximity of the eastern Transylvanian basin basement increased the heat flow, generating lateral salt extrusion, diapirism and increased pressure in the gas reservoir. New pathways were opened that provided new circulation routes for basinal fluids to new and old permeable zones and expelled seeps from the biogenic petroleum system.

Nitrogen influx was identified in the Harghita Bãi area, where the mechanism of NH4+-fixation in illitic clays is relevant for the N-input budget estimation. The nanotextural features of K-illite (K-I), NH4,K-I and NH4-illite-smectite (NH4-I-S) mixed layers observed in argillic-altered andesitic rocks from the hydrothermal area of Harghita Bãi (East Carpathians) were studied by X-ray diffraction, infrared spectroscopy and transmission and analytical electron microscopy (TEM-AEM). The texture of undisturbed argillic-altered andesite rocks exhibits chaotic intergrowths of randomly oriented and curved illitic packets with abundant pore spaces and high porosity between packets. The TEM images of K-I and NH4,K-I intergrowths show subparallel packets with clear contacts, exhibiting a diffuse contrast across layers. The thicknesses of K-I and NH4,K-I packets range from 150 to 500 Å, and 1Md and 1M polytypes were identified by selected area electron diffraction patterns. Crystal chemistry of K-I, NH4,K-I and NH4-I-S was carried out by AEM. A third interlayer cation Na+ beside K+ was detected in several NH4,K-I packets. The NH4,Na,K-I packets interleaved with NH4,K-I or NH4-I-S (12% smectite layers) packets were also identified by TEM. The thicknesses of NH4,Na,K-I packets range from 300 to 1200 Å, with abundant lenses and lenticular layer separation along the boundaries between them. The 1Md polytype dominates the NH4,Na,K-I packets. Straight and parallel packets, continuous 00l layers and collapsed swelling layers at the boundary of individual NH4-I (5% smectite layers) packets with thicknesses ranging from 20 to 95 Å were observed. The nanotextural observations indicate direct crystallization of NH4-I crystals within a NH4-I-S series from a pore fluid, where NH4-I packets occupy void spaces previously occupied by fluids.

Ammonium illite and ammonium illite-smectite mixed layers, together with potassium illite, smectite and minute amounts of kaolinite were identified in hydrothermally altered andesite rocks from the Harghita Bãi area of the Eastern Carpathians, Romania. K-Ar dating and oxygen isotope tracing, as well as rare-earth elemental analyses were made to provide new information on the timing and crystal-chemical processes characterizing the crystallization and further evolution of these illite-type mineral phases.

The combined results suggest the occurrence of hydrothermal activity in two distinct episodes with nucleation of two generations of illite-type particles of different chemistry and morphology. About 9.5 Ma ago, potassium illite crystallized in alteration halos of the porphyry Cu system, probably at a temperature of ~270ºC from fluids having a δ18O of ~2.9% (V-SMOW). Associated smectite seems to have precipitated slightly later in external alteration halos at a similar temperature, but from fluids depleted in alkalis and with a different δ18O. Alternately, ammonium-rich illite-smectite mixed layers formed very recently, less than ~1 million years ago at a temperature of ~90ºC from fluids of probable meteoric origin that altered the previously crystallized potassium illite, resulting in the crystallization of a new generation of ammonium illite-smectite mixed layers. Evidence of this dissolution-precipitation process is provided by a significant increase in the δ18O of the mixed-layer structures and by a significant change in their REE contents and distribution patterns. Occurrence of potassium in the ammonium-rich mixed layers probably relates to the progressive alteration of the first-generation potassium illite and a discrete concomitant take up of released K by the new NH4-rich interlayers of the ammonium mixed layered sequence.